Metalliferous azo dyestuffs



Patented July' 16, 1940 METALLIFEROUS AZO DYESTUFFS Joseph Gyr, Basel,Switzerland, assignor to Society of Chemical Switzerland Industry inBasie, Basel,

No Drawing. Application March 31, 1938, Se-

rial No. 199,277.

1937 4 Claims.

This invention relates to the manufacture of metalliferous poly-azodyestuffs of the formula in which a: and 11/ stand for a member of thegroup of the group consisting of H and -N=NRs, R3 standing for anaromatic isocyclic nucleus consisting of at least 6 and at the mostcarbon atoms, R1 stands for an aromatic isocyclic nucleus consistingofat least 6 and at the most 10 carbon atoms and containinginortho-position to the N=Ngroup a hydroxyl-group, R2 stands for anaromatic isocyclic nucleus consisting of at least 6 and at the most 10carbon atoms, and in which'one of the aryl radicals linked to the NH-group carries at least one sulfo group, by coupling 1 molof ameta-dihydroxy-- or meta-aminohydroxyor meta-diamino-compound of thebenzene series which is" capable of coupling at least twice, in anyorder with a diazo-compound containing at least one lake-forming groupand with a diazo-azo-compound obtainable by coupling a diazotizedaminodiphenylamine sulfonic acid with any desired middle component andfurther,

- preferably copper compounds, are to be made or used by the presentinvention, there come into question as aromatic amines (R1) containinglake-forming groups amines of the benzene and naphthalene series,wherein there is a hydroxyl group in ortho-position to the amino group;such amines are, for axample, ortho-aminophenols,

ortho-aminonaphthols, amino-salicylic acids, as well as the sulfonicacids, nitro,'alkyl and halogen substitution products of these bodies.As parent materials for the residues there may be used, for example,1:3-dihydroxybenzene, 1:3-diaminobenzene, 1-ami-no-3-hydroxybenzene, aswell as their substitution prod- 55 ucts insofar as these are capable ofcoupling at least twice. As parent materials for the residue R2 therecome into question so-called middle components, such as l-aminobenzene,l-amino-Z- methylbenzene, 1-an1ino-Z-methoxybenzene (in 60 the form oftheir w-methanesulfonic acid), 1-

consisting of OH and NH2, 2 stands for a member In Switzerland April 3,

amino-3-methylbenzene, 1-ainino-2:5-dimethylbenzene, l-amino-2-methoxyor-ethoxy-5 methylbenzene, l-amino-2:5-dimcthoxyor diethoxybenzene, 1amino-3-acetylaminobenzene,

l-aminonaphthalene, l-amino-Z-methoxyor -ethoxynaphthalene and their6-,or 7-sulfonic a c i d s, 2-amino-5-hydroxynaphthalene7-sulfonic acid,2-amino-8-hydroXynaphthalene-6 sulfonic acid or the like and as parentmaterials for the residue 4-amino-4-nitrodyphenylamine-2'-sulfonic acid,l-amino-Z-nitrodiphenylamine-4'-sulfonic acid, hairline-2' :6dinitrodiphenylamine 4- sulfonic 7 acid, 4amino-3-ethoxyor-methyl-4-nitrodiphenyla-mine-2'-sulfonic acid, 4-amino-2':4dinitrodiphenylami-ne-3-sulfonic, acid, 4'-aminodiphenylamine-2-sulfonic acid, 4-amino-4'- methylori-methoxy-diphenylamine-2esulffonic' acid or the like. As parentmaterial for the residue 2; insofar as it is not hydrogen, any diazo ordiazo-azo-compound may be used.

The azo dyestufis of the foregoing general formula may be produced bythe action of the any order and according to the selected. order as wellas the nature of the diazo compounds, the

coupling may occur in neutral, acid or alkalinemedium, for example in asolution containing sodium carbonate, bicarbonate, alkaline earth,caustic alkali, ammonia, pyridine, acetic acid or hydrochloric acid. betreated with various agents yielding metal, especially copper, forintroducing metal; suitable agents are copper sulfate, copper chloride,te'traniine-cupric sulfate, copper acetate,- any of which may be used,if desired, in the presence of an organic base, for instance pyridine.The agent yielding copper may be caused to act either on the mono-azodyestuff containing the lake-forming groups or on the finished disorpolyazo dyestuilf; furthermore, the treatment with copper may be appliedin the dyebath or simultaneously with the production of the dyestuff. Asother suitable metals there may. be named chromium, iron, nickel andcobalt, which also may be introduced into the dyestufi molecule byknownmethods.

The metalliferous azo dyestuffs obtainable by this invention areexcellent dyestuffs for leather and dye leather tanned in any manneruniform brown to black-brown tints. These dyeings are very fast to acidsand alkalis and of excellent fastness to light. They are characterizedby a good penetration.

The following examples illustrate the invention, the parts being byweight:

diam-compound on the coupling components in.

The dyestuff produced may Example 1 18.9 parts of2-aminophenol-4-sulfonic acid are N02 '1 CH3 HO on in presence of sodiumacetate with a solution of 13.7 parts of 1-methyl-3-amino-4-methoxyben--zene and diazotizing the mono-axo dyestuff thus formed. When theformation of dyestuff is complete, the Whole is heated to 70 C. and thedyestuff which represents the copper compound of the product of theformula OCH:

OiN

. SOaH CH3 HO salted out with sodium chloride. It dyes chrome leatherand vegetable tanned leather deep brown tints. Nickel and iron compoundsproduce also brown tints on chrome leather.

If in this example instead of the 4-nitro-4-aminodiphenylamine-Z-sulfonic acid there is used the same quantity of2-nitro-4-aminodiphenylamina-Q-sulfonic acid, the dyestuff ob- SOaH S0511 CH3 tained which represents the copper compound of the product ofthe formula OOH:

dyes chrome leather or vegetable tanned leather tints of a somewhat moreviolet strain.

Example 2 One of the trisazo dyestufis obtainable as described inExample 1 is coupled in solution alkaline with sodium carbonate with thediazo- 15 compound obtained by diazotizing 13.8 parts ofl-nitro-l-aminobenzene. When the formation of dyestufi is complete, thedyestuff which corresponds to the copper compound of the product of theformula 7 20 is salted out in usual manner with common salt. It dyeschrome leather. and vegetable tanned leather somewhat more yellowishtints than are produced by the dyestufi of Example 1. A similar dyestufiis produced when the diazocompound from 13.8 parts of4-nitro-1-aminobenzene is exchanged for that from 22.3 parts ofl-aminonaphthalene-lor -5-sulfonic acid.

Further diazotizing components which may be 45 used instead of theforegoing are, for example, those from l-chloro-l-aminobenzene,3-nitro-1- aminobenzene, l-aminobenzene-4=-sulfonic acid,l-amino-Z-methy1-4-chlorobenzene, 4'-nitro-4-'aminodiphenylamine-2'-sulf0nic acid; similar 50 products are obtained.Such dyestuffs are for example the copper, iron or nickel compounds ofthe dyestuffs of the formulas 0am soar: v

OH 0;]?! 25 v Example 3 The'complex copper compound obtained asdescribed in Example 1 from 18.9 parts of 2-aminophenol--sulfonic acidand 11 parts of 1:3-dihydrox benzene is dissolved in an excess of sodiumcarbon te solution. The solution is coupled with the diazo-azo-compoundobtainable by coupling the diazo-compound from 30.9 parts of 4-nitro-4-aminodiphenylamine-2-sulfonic acid in presence ofsodium acetate with asolution of 22.3 parts of l-aminonaphthalene-S- or -7-sulfonic acid andfurther diazotizing the monoazod-yestuff thus formed. When the formationof dyestuff is complete, the whole is heated to 70 C. and the dyestuifsalted out by sodium chloride. The dyestuff which represents the coppercompound of the product of the formula The formula of such a dyestufl isfor example the formula H solH 0311 v l HO OH N OaH Examples! The coppercompound obtained as described in Example 1 from 18.9 parts of2-amino-1-hydroxybenzenel-sulfonic acid and 11 parts of 1:3-d1-hydroxybenzene is dissolved in excess of sodium carbonate solution. Thesolution is coupled with the diazo-azo-compound obtainable by couplingthe diam-compound from 30.9 parts of 4'-nitro-4-aminodiphenylamine-2'-sulfonic acid in presdyes chrome leather andvegetable tanned leather deep brown tints. Iron and nickel compounds ofthis dyestuff dye similar tints.

'If in this example instead of the 4-nitro-4-aminodiphenylamine-2'-sulfonic acid there is used the same weight of2'-nitro-4-aminodience of sodium acetate with a solution of 14.3 partsof l-aminonaphthalene and further diazotizing the monoazo dyestufi thusobtained. When the formation of dyestuff is complete, the whole isheated to 70 C. and the dyestuff which represents the copper compound ofthe product of the formula OB v 1 SOaH HO- OH 80311phenylamine-4-sulfonic acid, the dyestuff obtained dyes chrome leatheror vegetable tanned leather tints of a. somewhat more violet strain,whereas. the copper compound of the dyestuif from the4-methy1-4-aminodiphenylamine-2- sul'fon'ic acid of the formula dyesdark violet brown'tints.

Somewhat redder dyestuffs are produced if in soul E0 the production ofthe monoazo dyestuff which is 'used asthe parent material for making thetrisazo dyestuffs of the first and second paragraphs of this examplethere'areused 23.4' parts of Z-aminol-nitro-1-hydroxybenzene-6 sulfonicacidinstead ofthe im arts of2-aminophenol-4-sulfonic a'cid'.

precipitated by addition of sodium chloride. It dyes chrome leather andvegetable tanned leather reddish brown tints.

Also in this example the 4'-nitro-4-aminodiphenylamine-2'-sulfonic acidcan be replaced by an unnitrated compound or the 4-CH3-compound. Such a.dyestuff is for example the cop- 03H HO OH 05H per, iron, nickel orcobalt compound of the product of the formula 0 11 HQ on Example 5 ofdyestuif is complete, the dyestuff is salted out with sodium carbonate;it represents thecopper compound of the product of the formula 303E HO VS 0 3H and dyes chrome leather and vegetable tanned leather somewhatmore yellowish tints than those OzNQNH 03H obtained with the dyestuffsof Example 3 or 4. Here also further similar dyestuffs can be made byusing the diazotizing components mentioned in the second paragraph ofExample 2.

Example 6 The dyestuff obtained by coupling the diazo compound from 23.9parts .of l-amino-Z-hydroxynaphthalene-l-sulfonic acid with 11 parts oflz3-dihydroxybenzene in caustic alkaline solution is precipitated byacidifying, re-dissolved in an excess of sodium carbonate solution and.coupled with the diazo-azo-compound obtainable by coupling thediazo-compound from 30.9 parts of4'-nitro-4-amino-diphenylamine-2-sulfonic acid in presence of sodiumacetate with a solution of 22.3 parts .of l-aminonaphthal'ene-B- (or-'7). -sulfonic acid and further diazotizing the monoazo dyestuff thusformed. When the formation of dyestuff is complete the dyestuff issalted out by sodium chloride, re-dissolved in hot Water, acidified withlittle acetic acid and boiled l for some time after addition of asolution of 25:- parts of crystallized copper sulfate. The dyestuff issalted out with sodium chloride. It represents the complex coppercompound of the product of the formula SOaH and dyes chrome leather andvegetable tanned leather deep brown tints.

A dyestufi having similar properties is obtained if the dyestuff iscoupled, previous to its conversion into the copper compound, with thediazo compound from 13.3 parts of 4-nitro-1-aminobenzene in thepresence-ofsodium carbonate and converted only subsequently, in -.theindicated (SH-1 v I soiHM- manner into the copper compound of theproduct of the formula 1 SOzH o l v Example H Neutralized chrome leather(box calf, chrome sides, glazed kid, full chrome sheep) is tumbled in acask with3-4 times its weight of water at 60 C. During the rotation,there is fed through the hollow-axle a solution of the cupriferousdyestuff obtained as described in Example 1. 40 minutes the dyestuff isabsorbed by the leather,

whereupon the latter is stuffed as usual.

The leather dyed-in this manner has a very full dark brown tint which isvery fast.

Example 8 Well fulled vegetable tanned sheep or goats leather is dyedneutral as described in Example 7. When the dyeing is complete,thereisladdad After about formic acid amounting to half'the weight ofthe dyestufi used and dyeing is continued for 10-15 minutes; rinsingfollows. 1

The dyed leather is deep-fast brown. Dyeing may also .be conducted in aneutral cold liquor by the brushing process.

What I claim is: 1. Cupriferous azo dyestuffs of the formula N=N-R inwhich a: and y stand f ora rnemberof the group consisting of: and standsfor stands for an aryl radical of the group consisting dyestuflz' of theformula 3. The complex copper compound of the azo HO OH soul of phenyland naphthyl radisals, one of the aryl in which one :1: stands for H andthe other a: for

radicals linked to the -N-group t carrying at .least one sulfo group;

2. The complex copper compound of the am dyestufi of the formula II NNO:

SOaH.

dyestufi of the formula SOsH.

SOaH

in which one :1: stands for H and. the other a: for

in which one :0 stands for H and. the other a: for

JOSEPH GYR.

